Vitreous enamel organosols



Patented Aug. 24, 1937 VITREOUS ENAMEL ORGANOSOLS Rudolph S. Bley, Elizabethton, Tenn, assignor to The Porcelain Enamel and Manufacturing Company of Baltimore, Baltimore, Md., a corporation of Maryland No Drawing. Application December 31, 1935, Serial No. 56,908

15 Claims.

The present invention relates to the production of vitreous enamel organosols which may be applied to metal bases by spraying, dipping, etc.

One object of my invention has to do with a vitreous enamel organosol, the liquid phase of which comprises an organic silicon compound.

Another object of my invention relates to the production of vitreous enamel organosols, the solid phase of which is dispersed in an aromatic silicon compound.

A third object of my invention has to do with a vitreous enamel organosol comprising a finely divided vitreous enamel frit dispersed in a liquid alkyl derivative of silicon.

A fourth object of the present invention relates to the manufacture of finely divided, vitreous enamel frit dispersed in tetraethyl-monosilane with or without the assistance of a protective colloid.

A fifth object of this invention has to do with the addition of protective colloids to the organosols, set forth above, to promote floating of the solid phase in the liquid phase of the organosol.

Other objects of my invention will become apparent to those skilled in the art from a study of the following specification.

Vitreous enamel, in reality a glass composition of a relatively low fusibility, is principally com posed of silicates, borates, fluorides, etc. In producing such vitreous enamel, so-called glassforming substances are mixed with auxiliary substances in certain definite proportions to form a composition which, subsequently, is fused and quenched in water. The product, obtained after quenching, is called in the art enamel frit. This frit is ground in water, containing clay, to a fine composition, the so-called vitreous enamel slip which may be applied to metal bases by spraying or dipping.

The aforementioned glass-forming substances are the following:

(1) Raw materials for introducing acid oxides (silicon, boron) (2) Raw materials for introducing basic oxides (soda, potash, lime, magnesia, lead oxide, etc.)

(3) Raw materials for introducing acid and .basic oxides (borax, fluorspar, kaolin,

etc.)

, The auxiliary substances, set forth above, are the following:

; (1) oxidizing agents (sodium nitrate, etc.) E (2) Adhering oxides (cobalt, nickel, manganese oxides, etc.) (3) Opaciflers (phosphates, fluorides, pigments, etc.)

Heretoiore, vitreous enamel slips have been 60 prepared by milling enamel frit with water containing about 7% of clay to a fine consistency, said clay being added to float the frit particles by hydration. This method, however, is unsat- *sfactory for the reason that frit particles give off 'a number of alkaline compounds in the presence of water. These alkaline compounds thin out the clay of the enamel slips, and as a. result the clay loses its floating property. Thus, the frit and clay particles settle in very short periods of time, and it becomes impossible to maintain a proper consistency of the enamel slip. A number of methods have been introduced to maintain or restore the consistency of enamel slips, 1. e.,

enamel hydrosols. Acid salts, for example, magnesium sulphate, are added to enamel slips to neutralize the alkaline compounds generated by the frit particles. Although the colloidal magnesium hydroxide, produced by chemical interaction of magnesium sulphate and said alkaline compounds, somewhat assists in floating enamel particles, this so-called setting up of aqueous enamel slips has proven unsatisfactory. Another method consists in adding buffer solutions to vitreous enamel slips to neutralize the alkalis, originating from the frit particles, to maintain the original, optimum pH values of such slips. Although this method, set forth in my application, Ser. No. 548,712, filed July.3, 1931, gives satisfactory results, I have found that it is extremely difficult to permanently set up a stainless enamel frit ground in water. In addition, such enamel hydrosols form rust on metal bases to which they are applied before firing, and as a results of such rusting so-called mottled coatings are obtained. Experimentation with enamel hydrosols proved that such rusting of metal bases is caused by the alkaline compounds dissociating in the presence of water to active anions and cations. To completely overcome this deficiency,

it is necessary to disperse frit particles in nonor very little conducting, organic liquids. In this manner the troublesome OH groups of alkalis are eliminated, i. e. inactivated.

I am well aware that it has heretofore been proposed to suspend special types of enamels in oils, and to fuse such oil-enamel suspensions on metal bases, such as silver, gold, etc. However, I have found this method to be unsatisfactory for enameling iron, steel, etc., for the reason that oils burn out with the formation of gases and finely divided soot. The gases and soot, escaping from the enamel coating upon fusing, tend to cause the formation of uneven enamel coatings covered with so-called pin-holes. Unexpectedly, I have found by experimentation that excellent, even vitreous enamel coatings can be produced by dispersing enamel frit in such organic liquids which do not only prevent the formation of acpromote the adherence of fused enamel frit to duced which resists the action at acids such as metal baseswhilesblending therewith. z contained in lemon Juice, for exam These In accordance with my present invention, I acid-resistant enamels, the so-called stainless disperse vitreous enamel frit in organic silicon enamels, are low in, or entirely free from, alu- 6 compounds which are liquid, anhydrous and stamina and. high in -silica content (up to 60% silble at ordinary room temperatures. When an ica). These stainless enamels will rapidly settle enamel irit is milled with such organic silicon their solid phases in water'due to large amounts compounds or dispersed therein, in the total abof alkaline compounds dissolving from the frit sence of water, the alkaline compounds, generatlparticles. Finally, the clay-enamel Pension 10 ed by the frit, do not form electrolytes with the becomes thinner and thinner, and the solid silicon compounds, the latter being practically phases settle to a dense, hard mass. In addition, non-conducting in anhydrous form. when such "when such slips are applied to iron or steel bases, an organosol, consisting of finely divided frit in they rust these metalsin -very short periods of organic silicon compounds, is applied to iron or time, and it becomes impossible to produce a steel plates, these plates are not corroded. 'I'hereclear one-coat enamel on iron or steel, etc. In fore, the enamel coatings do not become mottled order to' produce a clear white coating of enamel, on firing and the formation of a pure, white for example, on metal or steel, it is necessary to coating, for example, is assured. In addition, the fuse several layers of white enamel onto these silica formed upon firing the enamel slip onto the metals to camouflage the rust spots of the first metal base promotes the adherence of the enamel enamel coating. I

to said base. I. am well aware that attempts have, hereto- I have found that all such organic silicon comv fore, been made to overcome the tendency of pounds may be used which are liquid and stable stainless enamels to rust ironand steel bases to at ordinary room temperatures, or which are which they are applied. U. 8. Patent No.c 1,785, solid and soluble in other liquid, organic liquids. 777 to Kinzie of December 23, 1930, for example, Thus, I may use aliphatic, carbocyclic and hetdiscloses the addition of titanium sulphate to erocyclic silicon compounds having the aforestainless enamel slips to neutralize the alkalis mentioned properties. The following table degenerated by the same. However, this method picts a number of organic silicon derivatives does not allow complete prevention of rust forwhich may serve as liquid phases in the producmation on iron and steel, and it is necessary to tion of vitreous enamel organosols. form at least two coatings of enamel onsuch' Table Compound Structural formula gg g f 30-31 101 151-153 40 1:::::::::::::::::::: $3 ans-214 170-17] Tetragropyl-monosilane 213-214 Triiso utyl-monosilane 114-316 Isoamyl-monosilane 245 Tetraisoamyl-monosilane 275-279 'Irlethyl-monosilanol 154 Tnethyl-monosllanol-ethyl-ester 153 Triethyl-monosilanol acetate. 168 Silicoheptyl bromide 161 Sllleoheptyl oxide 23 Prop lanai m Tripropyl-monosilanol mil-m 'lripropyl-monosllanol-acetate 212-216 Tripro fyl-monosilyl-hromide 213 Bis-(t propyl-monosilyD-ether. 280-290 Triisoamyl-monosilanol 260-270 Trilsoamyl-monosilyl-bromide. C|Hn):SiBr 278-m Bis-(triisoamyl-monosilyD-ether C H11);Si.O.S i(OiH 360-370 Diethyl CgH )gsl.0.sl(CIHI)i--- Sllico-diethyl-ether (c m),si(o.c,n ggliaia-ghgfiogigicgfiglhlgiy-diethyl-monosilane o-Silicoacetic acid-methyl ester. o-Silicoacetic acid-trimethyl eaten.-.

o-Silicopropionic acid-triethyl ester o-Silicogropionic acid-triehloride. o-Sillco utyrlc acid-trichloride. O-Sillcolsocaproic acld-triethyl-estcr. Hexaethyl-disilane Pmpyl-mnnnsilandinl Isobutyl-monosilandiol Trichloro-ethyl-monosilane. 'Irichlororop l-monosllane.

'Irichlorouty -monosilane 0411.01;Si:CH|.CHg.CH .SiOli Trichloro-isobutyl monosilane- C H|Cl1Bi:(GH;) OH.CH|.SiCli 138-143 Trichloro-isoamyl-monosllane CsHu ls .SlCl 50 Hexamethyl-dlsilane a 112-114 Phenylsilioon chloride sHs 1W Phen lsllleon-triethyl ester. 35 811100 nzolc acid 127 Silicon triethyl-triphenyl- -166 Silicon triethylhenyl-chlorld zoo-20s Silicon di bony -chioridc- 230-237 Silicon t phenyl-chloride 88-89 p-Silloon tolyl-chlorlde ILS-fll and other aliphatic and aromatic silicon derivatlves having the characteristics set forth above.

metals to overcome themottling effect of stainless enamel. Yet, I have-found that it is possible In recent years, vitreous enamel has been proto form a sin l W n m M 8 r n and steel provided the frit particles are not suspended in aqueous media but in anhydrous, or-

ganic silicon compounds. Although it is possible to disperse the frit in such silicon compounds without any further additions thereto, I have found that the settling of the frit particles may be prevented for relatively long periods of time with the assistance of suitable protective colloids. Naturally, it is impossible to use such protective colloids which act in a hydrated form, such as gelatine, agar, alginates, etc., but I have found that oil-soluble soaps, such as barium, strontium, magnesium soaps, etc., produced by causing a metal salt to react with fatty acids, will effectively assist the floating of stainless enamels in organic silicon compounds. In addition, soaps formed by chemical interaction of naphthenic acids with metal salts are suitable protective colloids for the aforementioned purpose. However, I wish to emphasize that only such soaps can be used which are somewhat soluble in organic silicon compounds. The use of such protective colloids is naturally not limited to stainless enamel frits since any enamel frit will remain in suspension for longer periods of time in the presence of such colloids.

The amounts of vitreous enamel frit to be milled with or suspended in a given amount of a liquid organic silicon compound may be varied at will to form more or less viscous organosols to which clay, protective colloids, etc. may be added. Solid organic silicon derivatives may be dissolved in liquid ones, or they may be dissolved and/or emulsified with other stable, organic liquids, such as hydrocarbons, vegetable, mineral oils, etc., these liquids being called inert diluents. The finished organosols may be applied to metal bases, etc., by spraying or dipping. Before firing, the moist enamel layer is air-dried. This drying is preferably carried out in chambers which allow recovery of the vapors of the silicon derivatives by condensation, absorption, etc.

I desire to point out that all ingredients of my vitreous enamel organosols must be anhydrous, i. e., free from water, to prevent the formation of metal-corroding ions. Modifications of my process will readily be recognized by those skilled in the art, and I desire to include all such modifications falling within the scope of the appended 50 claims.

I claim:-

1. An organosol comprising a finely divided vitreous enamel frit uniformly dispersed in a liquid organic silicon compound, said compound 55 being anhydrous and stable at ordinary room temperatures.

2. An organosol comprising a finely divided vitreous enamel frit uniformly dispersed in a liquid aliphatic silicon compound, said compound 60 being anhydrous and stable at ordinary room temperatures.

3. An organosol comprising a finely divided vitreous enamel frit uniformly dispersed in a liquid aromatic silicon compound, said compound .65 being anhydrous and stable at ordinary room temperatures.

4. An organosol comprising a finely divided vitreous enamel frit uniformly dispersed in a liquid alkyl derivative of silicon, said derivative 70 being anhydrous and stable at ordinary room temperatures.

5. An organosol comprising a finely divided enamel frit dispersed in anhydrous tetraethylmonosilane.

6. An organosol comprising a finely divided vitreous enamel frit uniformly dispersed in a liquid organic silicon compound and an organic diluent, said compound and said diluent being anhydrous .and stable at ordinary room temperatures.

7. An organosol comprising a finely divided vitreous enamel frit uniformly dispersed in a liquid aliphatic silicon compound and an organic diluent, said compound and said diluent being anhydrous and stable at ordinary room temperatures.

8. An organosol comprising a 'finely divided vitreous enamel frit uniformly dispersed in a liquid aromatic silicon compound and an organic diluent, said compound and said diluent being anhydrous and stable at ordinary room temperatures.

9. An organosol comprising a finely divided vitreous enamel frit uniformly dispersed in a liquid alkyl derivative of silicon and an organic diluent, said derivatives and diluent being anhydrous and stable at ordinary room temperatures. L 10. An organosol comprising a finely divided vitreous enamel frit uniformly dispersed anhydrous tetraethyl-monosilane, said tetraethylmonosilane being diluted with an anhydrous organic liquid.

11. An organosol comprising a finely divided vitreous enamel frit uniformly dispersed in a liquid organic silicon compound with a soap of the group consisting of heavy metal soaps and naphthenic acid soaps, said compound and soap being anhydrous and stable at ordinary room temperatures.

12. An organosol comprising a finely divided vitreous enamel frit uniformly dispersed in a liquid aliphatic silicon compound with a soap of the group consisting of heavy metal soaps and naphthenic acid soaps, said compound and soap being anhydrous and stable at ordinary room temperatures.

13. An organosol comprising a finely divided vitreous enamel frit uniformly dispersed in a liquid aromatic silicon compound with a soap of the group consisting of heavy metal soaps and naphthenic acid soaps, said compound and soap being anhydrous and stable at ordinary room temperatures.

14. An organosol comprising a finely divided vitreous enamel frit uniformly dispersed in a liquid alkyl derivative of silicon, with a soap of the group consisting of heavy metal soaps and naphthenic acid soaps, said derivative and soap being anhydrous and stable atordinaryroom temperatures;

15. An organosol comprising a finely divided vitreous enamel frit uniformly dispersed in anhydrous tetraethyl-monosilane with the assistance of an anhydrous soap of the group consisting of heavy metal soaps and naphthenic acid soaps, said soap being stable at ordinary room temperatures.

RUDOLPH S. BLEY. 

